Unexpected decomposition of the bis (trifluoromethylsulfonyl) amide anion during electrochemical copper oxidation in an ionic liquid

Ismail, Amr S.; Abedin, Sherif Zein El; Höfft, Oliver; Endres, Frank

doi:10.1016/j.elecom.2010.04.018

Cited by 27 publications

(10 citation statements)

References 15 publications

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“…Second, the deposition time to reach 1 m thickness is 135, 27, and 5.4 s for 1, 5, and 25 A dm −2 , respectively, which is much shorter than the 2 hours of continuous anodization reported in Ref. 31.…”

Section: D24mentioning

confidence: 96%

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Schaltin¹,

Brooks

Binnemans

et al. 2011

J. Electrochem. Soc.

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The electrochemical behavior of the low-melting copper salts ͓Cu͑MeCN͒ x ͔͓Tf 2 N͔ and ͓Cu͑PhCN͒ x ͔͓Tf 2 N͔ ͑x = 2-4͒, where MeCN is acetonitrile and PhCN is benzonitrile, is presented. In these compounds, the copper͑I͒ ion is a main component of the ionic liquid cation. Consequently, the copper concentration is the highest achievable for an ionic liquid and this permits to obtain a good mass transport and high current densities for electrodeposition. The cathodic limit of the ionic liquid is the reduction of copper͑I͒ to copper metal instead of the breakdown of the cation as in conventional ionic liquids. It is shown that pure, crack-free copper layers can be deposited from these copper-containing ionic liquids in unstirred solutions at current densities up to 25 A dm −2 .Ionic liquids are useful solvents for electrochemical applications because of their wide electrochemical window and the presence of intrinsic ionic charge carriers. 1-3 Examples of such applications are their use as electrolytes in batteries, in photovoltaic devices, and for the electrodeposition of metals. In all of these applications, good mass transfer is needed. However, as the viscosity of most ionic liquids is much higher than that of the most molecular solvents, the mass transport in ionic liquids is rather poor. Moreover, the mass transport is limited even further by the poor solubility of simple metal salts ͑e.g., chlorides͒ in most ionic liquids suitable for electrodeposition, except for the dicyanamide ionic liquids. 4-7 The limited solubility is due to the poor coordinating power of anions such as ͓BF 4 ͔ − , ͓PF 6 ͔ − , or bis͑trifluoromethyl-sulfonyl͒imide ͓͑Tf 2 N͔ − ͒.To increase the solubility, functionalized ionic liquids can be used. These ionic liquids have a built-in coordinating unit such as a nitrile group which can complex the metal ion, thereby increasing its solubility. 8,9 Another way to improve the solubility of metal ions in ionic liquids is to design ionic liquids with a metal complex as part of their composition. 10

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Section: D24mentioning

confidence: 96%

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Schaltin¹,

Brooks

Binnemans

et al. 2011

J. Electrochem. Soc.

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“…217 From another side, it was shown that copper electrodes su ciently decrease elecrochemical stability of RTILs with fluorinated ions. 218 There has recently been great interest in RTIL properties at the interface with carbonbased electrodes (amorphous carbon, graphite, carbide-derived-carbon, carbon cloth, nanocarbon composites etc) 27,179,[219][220][221][222] due to large amount of current and potential applications of these materials (see more detailed discussion on this subject later on in the manuscript).…”

Section: Electrochemical Stabilitymentioning

confidence: 99%

Ionic Liquids at Electrified Interfaces

2014

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“…[8] The electrochemical stability of am ediumc an be evaluated by the width of its electrochemical potential window.F or imidazolium-based ionic liquids, it is typicallyl imited by the reduction of the cation and the oxidation of the anion. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative potentials. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative po...…”

Section: Introductionmentioning

confidence: 99%

“…[1,2,[9][10][11][12][13][14][15][16] It depends of course on the ionic species [1,2,10,12,13,16] but also on the material of the working electrode [2,[10][11][12][13][14] and on the presence of impuritiesincluding water. [10,16,17] Several studies report on the electrochemical stability of ionic liquids [15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31] and especially neat imidazolium-based ionic liquids [15,21,[23][24][25] at very negative potentials. They mainly rely on quantum chemical calculations [15,21] or experimental investigations by NMR, [21,24,…”

Section: Introductionmentioning

confidence: 99%

NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂

et al. 2017

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Potential controlled electrolyses of [BMIm][NTf ] ionic liquid were performed at a gold cathode under nitrogen atmosphere. The structures of the major conversion products of the BMIm cation were elucidated on the basis of 1D and 2D nuclear magnetic resonance (NMR) analyses and gas chromatography (GC) analysis of the volatile compounds. Recombination of the imidazol-2-yl radicals, generated at the electrode by single electron transfer, leads to neutral diastereomeric dimers in equal proportions, with a faradaic efficiency of 80 %, while disproportionation of these radicals and/or reaction with hydrogen atoms adsorbed at the electrode generates a neutral monomer with 20 % faradaic efficiency. Both pathways also yield the N-heterocyclic carbene imidazolin-2-ylidene, which is involved in fast proton exchange with the parent BMIm cation. The reductive decomposition products of the BMIm cation are no longer detected if the pre-electrolysed sample is reacted with CO , which undergoes an indirect reduction and generates the carboxylate adduct.

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Unexpected decomposition of the bis (trifluoromethylsulfonyl) amide anion during electrochemical copper oxidation in an ionic liquid

Cited by 27 publications

References 15 publications

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Ionic Liquids at Electrified Interfaces

NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂

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Unexpected decomposition of the bis (trifluoromethylsulfonyl) amide anion during electrochemical copper oxidation in an ionic liquid

Cited by 27 publications

References 15 publications

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Electrodeposition from Cationic Cuprous Organic Complexes: Ionic Liquids for High Current Density Electroplating

Ionic Liquids at Electrified Interfaces

NMR Study of the Reductive Decomposition of [BMIm][NTf2] at Gold Electrodes and Indirect Electrochemical Conversion of CO2

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NMR Study of the Reductive Decomposition of [BMIm][NTf₂] at Gold Electrodes and Indirect Electrochemical Conversion of CO₂